Synthesis, functionalisation and post-synthetic modification of bismuth metal-organic frameworks

Area of Science:

• Materials Science
• Inorganic Chemistry
• Crystallography

Background:

• Bismuth metal-organic frameworks (Bi-MOFs) are an emerging class of porous materials with diverse applications.
• Developing new Bi-MOFs with tunable properties is crucial for advancing materials science.

Purpose of the Study:

• To discover and characterize new bismuth metal-organic frameworks (Bi-MOFs).
• To investigate the synthesis of functionalized Bi-MOFs and their post-synthetic modification.
• To explore the structural diversity of Bi-MOFs based on reaction conditions and linker functionalization.

Main Methods:

• High-throughput synthesis using bismuth(iii) nitrate pentahydrate and triazine-2,4,6-triyl-tribenzoic acid (H3TATB).
• Structure determination and refinement using Powder X-ray Diffraction (PXRD) data.
• Post-synthetic modification of amino-functionalized Bi-MOFs with various anhydrides and sultones.

Main Results:

• Two new Bi-MOFs, CAU-35 ([Bi2(O)(OH)(TATB)]·H2O) and CAU-7-TATB ([Bi(TATB)]·DMF·6H2O), were successfully synthesized and structurally characterized.
• A functionalized porous Bi-MOF, CAU-7-TATB-NH2 ([Bi(TATB-NH2)]·5H2O·0.5DMF), was obtained using an amino-functionalized linker.
• Post-synthetic modification of CAU-7-TATB-NH2 achieved conversion rates between 33% and 79% with different reagents.

Conclusions:

• The study successfully expanded the library of known Bi-MOFs through systematic synthesis and characterization.
• The developed functionalized Bi-MOF offers a platform for further chemical modifications, enhancing its utility.
• This work highlights the versatility of Bi-MOFs in materials design and functionalization.